TY - CHAP A1 - Eckert, Karl-Andreas A1 - Dasgupta, Sunanda A1 - Selge, Benjamin A1 - Ay, Peter T1 - Liquid solid phase behavior of ternary fatty acid systems of palmitic, stearic, oleic and linoleic acid T2 - Book of Abstracts of the 8th Workshop on Fats and Oils as Renewable Feedstock for the Chemical Industry Karlsruhe, March 29–31, 2015 N2 - Enrichment of natural unsaturated fractions by melt crystallization processes has already been proved to be effective in prior investigations [1]–[3]. Palmitic, stearic, oleic, linoleic and linolenic acid are the five main fatty acids present in most of these plant based natural oils. There is quite a bit of information about the liquid solid phase behavior of binary mixtures such as palmitic-oleic, stearic-oleic and palmitic-stearic acid mixtures in literature [4]–[6]. Recent investigations have shown phase diagrams of real natural oil based fatty acid systems containing up to 19% saturated content (11% stearic acid and 8% palmitic acid) [7]. Yet, there is hardly any information regarding ternary systems as those of palmitic-stearic-oleic and palmitic-stearic-linoleic acids. In this work, synthetic mixtures have been used in order to obtain a complete overview of the liquid solid phase diagrams of these ternary mixtures. To imitate naturally occurring mixtures, a mixture with 1:1 ratio of palmitic stearic acid was prepared. Varying amounts of either oleic or linoleic acids were added to this mixture in order to obtain the entire range required for the phase diagrams. These mixtures were then subjected to a specific profile with a wide temperature range in a Differential Scanning Calorimeter (DSC) so as to record every phase transition. This study successfully concludes that these complex mixtures could be treated as binary mixtures of their saturated and unsaturated contents. This is because there were essentially two main peaks noted in the DSC thermograms. It is to be noted that there was a third peak, assumed to represent the solid transition, in mixtures containing oleic acid. This has already been shown in detail and discussed in prior investigations [6], [7]. Another major discovery was that the solidus line depends on the type of the unsaturated content, that is, the degree of unsaturation, in the mixture. KW - Phase Diagram, Ternary Mixtures, Fatty Acids, Differential scanning calorimetry Y1 - 2015 UR - http://conferences.abiosus.org/abstract/show/630 UR - http://www.abiosus.org/Book_of_Abstracts_2015.pdf SP - S. 73 PB - abiosus e.V. Conferences CY - Karlsruhe, Germany ER - TY - CHAP A1 - Eckert, Karl-Andreas A1 - Dasgupta, Sunanda A1 - Ay, Peter T1 - Novel techniques to optically characterize melt crystallization kinetics of high oleic sunflower oil based fatty acid mixture T2 - Book of Abstracts of the 7th Workshop on Fats and Oils as Renewable Feedstock for the Chemical Industry Karlsruhe, March 23–25, 2014 N2 - The rising applications of enriched unsaturated fatty acid fractions are significantly increasing the need for a cheap method of manufacturing such fractions. Melt crystallization is an established method for purification and enrichment of desired fractions from mixtures [1, 2, 3]. Enrichment of such natural unsaturated fractions by melt crystallization processes has already been proved effective in prior investigations [1, 2]. Since then many analytical and investigative methods have been applied on various natural plant oil based poly-unsaturated fatty acid (PUFA) mixtures to generate the much needed fundamental melt crystallization data [1]. One such method is the use of in-situ polarized light microscopy [1, 4, 5]. Some of the important parameters affecting the melt crystallization of PUFA mixtures are nucleation and crystal growth rate. To be able to observe and visualize these micro-scale phenomena, circular polarized transmitted light microscopy was applied. A tempered chamber (Linkam LS 120) containing the sample between two object slides was placed right within the microscope camera setup (Leica DM RME and Leica DFC 500) with a viewing window. With respect to the transmitted light, the sample was placed between two circular polarized filters such that the system is calibrated for optimal visualization. Unlike linear polarization, in this method every crystal independent of its alignment in the sample, delivers an interference color different from its background. This way, the entire crystal structure could be clearly separated from the melt. Nucleation and crystal growth rate of a high oleic sunflower oil based PUFA was measured using this method at 5K supercooling and 10K/min cooling rate. Growth curves for total crystal area and number of crystals were analyzed and illustrated graphically. A typical S- curve is observed for both the cases starting with a lag phase followed by an exponential growth phase and ending in a saturation phase. KW - Polarized light microscopy, PUFA, melt crystallization Y1 - 2014 UR - http://conferences.abiosus.org/abstract/show/559 UR - http://www.abiosus.org/Book_of_Abstracts_2014.pdf PB - abiosus e.V. Conferences CY - Karlsruhe, Germany ER - TY - GEN A1 - Eckert, Karl-Andreas A1 - Dasgupta, Sunanda A1 - Selge, Benjamin A1 - Ay, Peter T1 - Solid liquid phase diagrams of binary fatty acid mixtures - Palmitic/stearic with oleic/linoleic/linolenic acid mixture T2 - Thermochimica Acta N2 - The solid liquid phase diagrams of binary mixtures of the five main saturated and unsaturated fatty acids present in most edible plant oils have been determined in this paper. These binary mixtures comprise of a saturated fatty acid, either palmitic (C16:0) or stearic (C18:0) and an unsaturated one, oleic (C18:1), linoleic (C18:2) or linolenic (C18:3) acid. Differential scanning calorimetry (DSC) was used to obtain an overview of the solid liquid transition behaviour including the metastable ranges of these mixtures. In order to describe all the phase transformations in these systems, the boundary functions have been determined and compared. Phase diagrams determined, illustrate characteristic behaviour in accordance to literature. This work specifically focuses on to describe the solid liquid transitions of the mixtures and not on every single transition or reaction. This paper contributes to the elucidation of the phase behaviour of these important mixtures which are applied in diverse industries. KW - Binary mixtures; Solid liquid equilibrium; Saturated and unsaturated fatty acids; Phase diagram; DSC Y1 - 2016 UR - http://www.sciencedirect.com/science/article/pii/S0040603116300193 U6 - https://doi.org/10.1016/j.tca.2016.02.008 SN - 0040-6031 VL - Vol. 630 SP - 50 EP - 63 ER - TY - GEN A1 - Eckert, Karl-Andreas A1 - Dasgupta, Sunanda A1 - Selge, Benjamin A1 - Ay, Peter T1 - Construction and comparison of solid liquid phase diagrams of binary sat-sat and unsat-unsat fatty acid mixtures comprising two of palmitic/stearic/oleic/linoleic/linolenic acid T2 - Journal of Environmental Research And Development N2 - In this paper, binary phase diagrams of the five main fatty acids present in edible oil based mixtures are shown. While previously the binary systems of one saturated and one unsaturated acid were investigated, in this work the binary mixtures comprise of palmitic (C16:0) and stearic acid (C18:0) or a binary mixture of oleic (C18:1), linoleic (C18:2) or linolenic acid (C18:3). In order to obtain the phase diagrams with all the solid liquid and solid phase transitions, the mixtures were analyzed by means of Differential Scanning Calorimetry (DSC). Phase change boundary functions based on thermodynamic models and experimental values were fitted and compared. The phase diagrams obtained show behaviors in good agreement to literature. The paper contributes to the deeper understanding of the essential phase change effects during industrial crystallization processes. KW - Binary mixtures KW - Solid liquid equilibrium KW - Saturated and unsaturated fatty acids KW - Phase diagram KW - DSC Y1 - 2016 UR - http://www.jerad.org/ppapers/dnload.php?vl=10&is=4&st=612 SN - 0973-6921 SN - 2319-5983 VL - 10 IS - 4 ER - TY - GEN A1 - Eckert, Karl-Andreas A1 - Dasgupta, Sunanda A1 - Selge, Benjamin A1 - Ay, Peter T1 - Novel model for the prediction of SSLE temperatures and crystallization paths of any mixture containing palmitic, stearic, oleic, linoleic and linolenic acid T2 - Thermochimica Acta N2 - A mathematical model for the prediction of phase change temperatures and crystallization paths for mixtures consisting of palmitic (P), stearic (S), oleic (O), linoleic (L) and linolenic acid (Ll) in any distribution is presented in this paper. This model is based on the information gathered from modeled ternary phase diagrams, namely PSO, PSL, PSLl and OLLl, that were based on experimental binary phase diagrams of all possible combinations of these fatty acids. These experimental binary phase diagrams were obtained by means of differential scanning calorimetry and mathematical function fitting, within which the eutectic region of binary palmitic/stearic with oleic/linoleic/linolenic acid was investigated in detail. The basic mathematical model used was previously shown in literature which delivered good results for such systems. The importance of the developed model was then justified by investigations on real and composed synthetic fatty acid mixtures, where a high accuracy of the predicted temperatures could be shown for the technically relevant liquidus and solidus temperatures. A satisfying prediction for thermal events below the first solidus line could be reached as well. This work directly contributes to an enhanced understanding of the thermodynamic and kinetic background of such important mixtures applied in diverse products and industries, thereby showing a large optimization potential for crystallization technologies. KW - Binary mixtures KW - Ternary mixtures KW - Solid liquid equilibrium KW - Saturated and unsaturated fatty acids KW - Phase diagram KW - DSC KW - Modeling Y1 - 2017 U6 - https://doi.org/10.1016/j.tca.2017.03.015 SN - 0040-6031 VL - 652 SP - 126 EP - 140 ER -